EP3464497A1 - Bande autoadhésive - Google Patents

Bande autoadhésive

Info

Publication number
EP3464497A1
EP3464497A1 EP17706433.4A EP17706433A EP3464497A1 EP 3464497 A1 EP3464497 A1 EP 3464497A1 EP 17706433 A EP17706433 A EP 17706433A EP 3464497 A1 EP3464497 A1 EP 3464497A1
Authority
EP
European Patent Office
Prior art keywords
pressure
sensitive adhesive
adhesive
weight
component
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP17706433.4A
Other languages
German (de)
English (en)
Other versions
EP3464497B1 (fr
Inventor
Axel Burmeister
Mathias HOSER
Franciska Lohmann
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Tesa SE
Original Assignee
Tesa SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Tesa SE filed Critical Tesa SE
Publication of EP3464497A1 publication Critical patent/EP3464497A1/fr
Application granted granted Critical
Publication of EP3464497B1 publication Critical patent/EP3464497B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/385—Acrylic polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/12—Chemical modification
    • C08J7/16—Chemical modification with polymerisable compounds
    • C08J7/18—Chemical modification with polymerisable compounds using wave energy or particle radiation
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/32—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof from compositions containing microballoons, e.g. syntactic foams
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0025—Crosslinking or vulcanising agents; including accelerators
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J11/00—Features of adhesives not provided for in group C09J9/00, e.g. additives
    • C09J11/08—Macromolecular additives
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/24—Plastics; Metallised plastics based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/241—Polyolefin, e.g.rubber
    • C09J7/243—Ethylene or propylene polymers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/20—Adhesives in the form of films or foils characterised by their carriers
    • C09J7/22—Plastics; Metallised plastics
    • C09J7/25—Plastics; Metallised plastics based on macromolecular compounds obtained otherwise than by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/255—Polyesters
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J7/00—Adhesives in the form of films or foils
    • C09J7/30—Adhesives in the form of films or foils characterised by the adhesive composition
    • C09J7/38—Pressure-sensitive adhesives [PSA]
    • C09J7/381—Pressure-sensitive adhesives [PSA] based on macromolecular compounds obtained by reactions involving only carbon-to-carbon unsaturated bonds
    • C09J7/383—Natural or synthetic rubber
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1804—C4-(meth)acrylate, e.g. butyl (meth)acrylate, isobutyl (meth)acrylate or tert-butyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/12—Esters of monohydric alcohols or phenols
    • C08F220/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F220/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C08F220/1808—C8-(meth)acrylate, e.g. isooctyl (meth)acrylate or 2-ethylhexyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2203/00—Applications of adhesives in processes or use of adhesives in the form of films or foils
    • C09J2203/326—Applications of adhesives in processes or use of adhesives in the form of films or foils for bonding electronic components such as wafers, chips or semiconductors
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/10—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet
    • C09J2301/12—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers
    • C09J2301/124—Additional features of adhesives in the form of films or foils characterized by the structural features of the adhesive tape or sheet by the arrangement of layers the adhesive layer being present on both sides of the carrier, e.g. double-sided adhesive tape
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/302—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier the adhesive being pressure-sensitive, i.e. tacky at temperatures inferior to 30°C
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/30—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier
    • C09J2301/312—Additional features of adhesives in the form of films or foils characterized by the chemical, physicochemical or physical properties of the adhesive or the carrier parameters being the characterizing feature
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2301/00—Additional features of adhesives in the form of films or foils
    • C09J2301/40—Additional features of adhesives in the form of films or foils characterized by the presence of essential components
    • C09J2301/412—Additional features of adhesives in the form of films or foils characterized by the presence of essential components presence of microspheres
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2400/00—Presence of inorganic and organic materials
    • C09J2400/20—Presence of organic materials
    • C09J2400/24—Presence of a foam
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2423/00—Presence of polyolefin
    • C09J2423/10—Presence of homo or copolymers of propene
    • C09J2423/106—Presence of homo or copolymers of propene in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2467/00—Presence of polyester
    • C09J2467/006—Presence of polyester in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2477/00—Presence of polyamide
    • C09J2477/006—Presence of polyamide in the substrate
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J2479/00—Presence of polyamine or polyimide
    • C09J2479/08—Presence of polyamine or polyimide polyimide
    • C09J2479/086—Presence of polyamine or polyimide polyimide in the substrate

Definitions

  • the invention relates to a pressure-sensitive adhesive strip.
  • Adhesive tapes are often used for the bonding of micro components, for example in devices in the consumer electronics industry. In order to make this possible, it is necessary for the shape of the adhesive tape section to be adapted to the shape of the component. In this case, often difficult geometries are necessary, which are obtained by punching the tape. For example, web widths of stamped parts of a few millimeters are not uncommon. When applying these sensitive tapes to the components, it often results in deformation of the stamped parts.
  • a film for example a PET film
  • the adhesive tapes as a middle layer in order to absorb the tensile forces during application.
  • Adhesions with such adhesive tapes are also increasingly used when the component is exposed to shock loads. Bonding with pressure-sensitive adhesive strips which have a viscoelastic, syntactically foamed core, a stabilizing film and two self-adhesive layers on the outer layers have proved to be particularly shock-resistant.
  • pressure-sensitive adhesive strips are so powerful that, under shock load, a cohesive break can be observed within the pressure-sensitive adhesive strip.
  • the bond between the foamed core and the stabilizing film fails, and foam and film separate from each other.
  • Foamed PSA systems have long been known and described in the prior art.
  • polymer foams can be produced in two ways. On the one hand by the action of a propellant gas, whether it is added as such or resulting from a chemical reaction, on the other hand by the incorporation of hollow spheres in the material matrix. Foams made in the latter way are called syntactic foams.
  • hollow spheres such as glass spheres or ceramic hollow spheres (microspheres) or microballoons are incorporated in a polymer matrix.
  • the voids are separated from one another in a syntactic foam and the substances (gas, air) located in the cavities are separated from the surrounding matrix by a membrane.
  • micro hollow balls foamed masses are characterized by a defined cell structure with a uniform size distribution of the foam cells.
  • closed-cell foams are obtained without cavities, which are distinguished, among other things by a better sealing effect against dust and liquid media compared to open-cell variants.
  • chemically or physically foamed materials are more prone to irreversible collapse under pressure and temperature, and often exhibit lower cohesive strength.
  • expandable microspheres also referred to as "microballoons” are used as microspheres for foaming.
  • such foams have a higher adaptability than those with non-expandable, non-polymeric hollow microspheres (for example They are more suitable for compensating for manufacturing tolerances, which are the rule, for example, in injection-molded parts, and because of their foam character they can also better compensate for thermal stresses.
  • the mechanical properties of the foam can be further influenced.
  • the foam has a lower density than the matrix, it is possible to produce foams having higher cohesive strength than the polymer matrix alone.
  • typical foam properties such as adaptability to rough substrates with a high cohesive strength can be combined for self-adhesive foams.
  • the devices in the consumer electronics industry include electronic, optical and precision mechanical devices in the meaning of this application, in particular such devices as those in Class 9 of the International Classification of Goods and Services for the Registration of Marks (Classification of Nice); 10th edition (NCL (10-2013)); in the case of electronic, optical or fine mechanical equipment, and in particular watches and timepieces in accordance with Class 14 (NCL (10-2013))
  • Acoustic recording, processing, transmitting and reproducing apparatus such as radios and the like
  • Remote communication and multifunction devices with remote communication function such as telephones, answering machines
  • the invention particularly preferably relates to mobile devices, since the pressure-sensitive adhesive strip used according to the invention has a particular benefit here due to the unexpectedly good properties (very high shock resistance).
  • very high shock resistance very high shock resistance
  • Cameras digital cameras, photography accessories (such as light meters, flash units, irises, camera housings, lenses, etc.), movie cameras, video cameras ⁇ small computers (mobile computers, handheld computers, calculators), laptops, notebooks, netbooks, ultrabooks, tablet computers, handhelds, electronic diaries and organizers (so-called “electronic organizers” or “personal digital assistants", PDA, palmtops), modems,
  • Radios also small and pocket radios
  • Walkmen also small and pocket radios
  • Discmen music players for example CD, DVD, Bluray, cassettes, USB, MP3, headphones
  • Mobile detectors • Mobile detectors, optical enlargers, remote vision devices, night vision devices ⁇ GPS devices, navigation devices, portable interface devices of the
  • the adhesive tapes do not fail in their holding performance when the electronic device, for example a cell phone, is dropped and impacts the ground.
  • the adhesive strip must therefore have a very high shock resistance.
  • the object of the invention over the previously published prior art is to find a pressure-sensitive adhesive strip having a particularly high shock resistance, in particular in the z-plane (ie in particular with respect to mechanical action perpendicular to the bonding plane).
  • the object is achieved with a generic pressure-sensitive adhesive strip according to the invention, as laid down in the main claim.
  • a layer SK1 of a self-adhesive mass which is arranged on top of the layer B and which is on a foamed self-adhesive
  • a layer SK2 of a self-adhesive mass which is arranged on the side of the layer F opposite the layer SK1 and which is likewise based on a foamed self-adhesive acrylate composition.
  • the film carrier is non-stretchable.
  • the inner layer F made of a film carrier is synonymously also referred to simply as a film carrier, film layer or as a film carrier layer.
  • the layers SK1 and SK2 of self-adhesive composition are also referred to as self-adhesive layers SK1 and SK2, simply as layers SK1 and SK2 or else as exterior layers, adhesive masses, self-adhesive masses or PSA layers SK1 and SK2.
  • the term "outboard” refers to the three-layered construction of the pressure-sensitive adhesive strip, without prejudice to possibly provided liners on the outer surfaces of the self-adhesive mass layers (see below).
  • one or both surfaces of the film layer F are physically and / or chemically pretreated.
  • Such pretreatment can be carried out, for example, by etching and / or corona treatment and / or plasma pretreatment and / or priming. If both surfaces of the film layer are pretreated, the pretreatment of each surface can be different or, in particular, both surfaces can be pretreated the same.
  • the invention is a pressure-sensitive adhesive strip of symmetrical design with regard to the composition of the layers, in that the foamed self-adhesive acrylate compositions of the two outer layers SK1 and SK2 are chemically identical and, advantageously, also if additives are added to them, they are identical and used in identical quantities.
  • a pressure-sensitive adhesive strip which is structurally symmetrical in the z direction but in which the outer self-adhesive layers SK1 and SK2 have the same thickness and / or the same density, but are chemically different as foamed self-adhesive acrylate mass layers.
  • the pressure-sensitive adhesive strip has a completely symmetrical structure, that is to say both with respect to the chemical composition of the two foamed self-adhesive acrylate mass layers SK1 and SK2 (including their optionally present additives), as well as with respect to its structural structure, in that both surfaces of the - in particular non-expandable - film carrier F identical pretreated and the two outer self-adhesive layers SK1 and SK2 have the same thickness and density.
  • “Fully symmetric” refers in particular to the z-direction ("thickness", direction perpendicular to the pressure-sensitive adhesive strip level) of the pressure-sensitive adhesive strip, but can beyond Of course, also refer to the geometry in the surface plane (x and y directions, ie length and width of the pressure-sensitive adhesive strip).
  • the self-adhesive acrylate compositions of the layers SK1 and SK2 are each a PSA (pressure sensitive adhesives).
  • PSA pressure sensitive adhesives
  • self-adhesive and pressure-sensitive adhesive are used interchangeably in the context of this document.
  • Pressure-sensitive adhesives are, in particular, those polymeric compositions which, if appropriate by suitable addition with other components such as, for example, tackifier adhesives, are permanently tacky and tacky at the application temperature (unless otherwise defined, at room temperature) and adhere to a large number of surfaces upon contact, in particular adhere immediately They are able to produce a substrate to be bonded even at the temperature of use without activation by solvents or by heat, but usually by the influence of a more or less high pressure To wet, so that between the mass and the substrate for adhesion sufficient interactions can form include the pressure and the contact time.
  • the special properties of the PSAs are due in particular to their viscoelastic properties.
  • weakly or strongly adhering adhesives can be produced; furthermore, those which can be glued only once and permanently, so that the bond can not be released without destroying the adhesive and / or the substrates, or those which are easily removable and, if necessary, can be glued several times.
  • Pressure-sensitive adhesives can in principle be produced on the basis of polymers of different chemical nature.
  • the pressure-sensitive adhesive properties are influenced inter alia by the nature and the proportions of the monomers used in the polymerization of the polymers on which the PSA is based, their average molecular weight and molecular weight distribution, and by the nature and amount of the PSA additives, such as tackifier resins, plasticizers and the like.
  • the monomers on which the PSA-based polymers are based, and optionally further components of the PSA are chosen such that the PSA has a glass transition temperature (according to DIN 53765) below the application temperature (ie usually below room temperature ) exhibit.
  • suitable cohesion-increasing measures such as, for example, crosslinking reactions (formation of bridging linkages between the macromolecules)
  • the temperature range in which a polymer mass has pressure-sensitive adhesive properties can be increased and / or shifted.
  • the scope of the PSAs can thus be optimized by adjusting the flowability and cohesion of the mass.
  • a PSA is permanently tacky at room temperature, so it has a sufficiently low viscosity and high tack, so that it wets the surface of the respective Klebegrunds already at low pressure.
  • the adhesiveness of the adhesive is based on its adhesive properties and the removability on their cohesive properties.
  • Adhesive compositions which can be used according to the invention
  • Acrylic-based adhesives based on solvents or on a water-based basis or else as a hot-melt system for example a composition based on acrylate hotmelt, which may have a K value of at least 20, in particular greater than 30, obtainable by the invention, can be used for the self-adhesive compositions SK1 and SK2 Concentrating a solution of such a mass to a hotmelt processable system.
  • the concentration can take place in suitably equipped boilers or extruders, in particular in the concomitant degassing a vented extruder is preferred.
  • the acrylate hotmelt based adhesive may be chemically crosslinked.
  • An adhesive which also shows to be suitable is a low molecular weight acrylate melt pressure-sensitive adhesive such as, for example, acResin® UV from BASF and acrylic dispersion pressure-sensitive adhesives, for example available under the trade name Acronal® from BASF.
  • acResin® UV from BASF
  • acrylic dispersion pressure-sensitive adhesives for example available under the trade name Acronal® from BASF.
  • self-adhesive compositions of (meth) acrylic acid and esters thereof having 1 to 25 carbon atoms, maleic, fumaric and / or itaconic acid and / or their esters, substituted (meth) acrylamides, maleic anhydride and other vinyl compounds such as vinyl esters, in particular vinyl acetate, vinyl alcohols and / or vinyl ethers used.
  • the residual solvent content should be below 1 wt .-% be carrying i.
  • Another preferred embodiment is a pressure-sensitive adhesive containing a polyacrylate polymer.
  • This is a polymer which is obtainable by radical polymerization of acrylic monomers, which are also understood to mean methylacrylic monomers, and optionally other copolymerizable monomers.
  • it may be a polyacrylate crosslinkable with epoxide groups.
  • functional monomers which can be crosslinked with epoxide groups, in particular monomers having acid groups (especially carboxylic acid, sulfonic acid or .alpha Phosphonic acid groups) and / or hydroxy groups and / or acid anhydride groups and / or epoxy groups and / or amine groups for use; preferred are carboxylic acid group-containing monomers.
  • the polyacrylate has copolymerized acrylic acid and / or methacrylic acid.
  • monomers which can be used as comonomers for the polyacrylate are, for example, acrylic acid and / or methacrylic acid esters having up to 30 carbon atoms, vinyl esters of carboxylic acids containing up to 20 carbon atoms, vinylaromatics having up to 20 carbon atoms, ethylenically unsaturated nitriles, vinyl halides, vinyl ethers of alcohols containing 1 to 10 carbon atoms, aliphatic hydrocarbons having 2 to 8 carbon atoms and 1 or 2 double bonds or mixtures of these monomers.
  • R 1 is H or CH 3 and R 2 is H or linear, branched or cyclic, saturated or unsaturated alkyl radicals having 1 to 30, in particular 4 to 18, carbon atoms,
  • component (i) optionally further acrylates and / or methacrylates and / or olefinically unsaturated monomers that are copolymerizable with component (i).
  • the proportions of the corresponding components (i), (ii), and (iii) are selected such that the polymerization product, in particular a glass transition temperature of less than or equal to 15 ° C (determined by DSC (differential scanning calorimetry) according to DIN 53 765 at a heating rate of 10 K / min).
  • the monomers of component (i) in a proportion of 45 to 99 wt .-%, the monomers of component (ii) in a proportion of 1 to 15 wt .-% and the monomers of Component (iii) in an amount of 0 to 40 wt .-% are especially plasticizing and / or nonpolar monomers.
  • acrylic monomers which comprise acrylic and methacrylic acid esters having alkyl groups consisting of 4 to 18 C atoms, preferably 4 to 9 C atoms.
  • examples of such monomers are n-butyl acrylate, n-butyl methacrylate, n-pentyl acrylate, n-pentyl methacrylate, n-amyl acrylate, n-hexyl acrylate, hexyl methacrylate, n-heptyl acrylate, n-octyl acrylate, n-octyl methacrylate, n-nonyl acrylate, isobutyl acrylate, isooctyl acrylate , Isooctylmethacrylat and their branched isomers such as 2-ethylhexyl acrylate or 2-ethylhexyl methacrylate.
  • monomers of component (ii) are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinylacetic acid, vinylphosphonic acid, itaconic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, hydroxypropyl methacrylate,
  • 6-hydroxyhexyl methacrylate allyl alcohol, glycidyl acrylate, glycidyl methacrylate.
  • Exemplary monomers for component (iii) are: methyl acrylate, ethyl acrylate, propyl acrylate, methyl methacrylate, ethyl methacrylate, benzyl acrylate, benzyl methacrylate, sec-butyl acrylate, tert. Butyl acrylate, phenyl acrylate, phenyl methacrylate, isobornyl acrylate, isobornyl methacrylate, t-butylphenyl acrylate, t-butylaphenyl methacrylate,
  • vinyl ethers such as vinyl methyl ether, ethyl vinyl ether, vinyl isobutyl ether
  • vinyl esters such as vinyl acetate, vinyl chloride
  • Macromonomers such as 2-polystyrene ethyl methacrylate (molecular weight M w from 4000 to 13000 g / mol), poly (methyl methacrylate) ethyl methacrylate (M w from 2000 to 8000 g / mol).
  • Monomers of component (iii) may advantageously also be chosen such that they contain functional groups which promote a subsequent radiation-chemical crosslinking (for example by electron beams, UV).
  • Suitable copolymerizable photoinitiators are, for example, benzoin acrylate and acrylate-functionalized benzophenone derivatives.
  • Monomers that promote electron beam crosslinking for example, tetrahydrofurfuryl acrylate, N-tert-butylacrylamide, allyl acrylate, but this list is not exhaustive.
  • composition of the PSA are epoxy-based crosslinkers.
  • multifunctional epoxides are used as substances containing epoxide groups, ie those which have at least two epoxide units per molecule (ie are at least bifunctional). These can be both aromatic as well as aliphatic compounds. Epoxy-based crosslinkers can also be used in oligomeric or polymeric form.
  • the mixture of acrylates may in turn preferably have the following composition:
  • the monomer (I) forms a mixture of 2-ethylhexyl acrylate and n-butyl acrylate, more preferably in equal parts.
  • Suitable monomers (II) are, for example, acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid and / or maleic anhydride.
  • the adhesive should be at its processing temperature above its glass transition temperature to have viscoelastic properties.
  • the glass transition temperature of the pressure-sensitive adhesive composition is therefore preferably below +15 ° C. (determined by DSC (differential scanning calorimetry) according to DIN 53 765 at a heating rate of 10 K / min).
  • the glass transition temperature of the acrylate copolymers can be estimated according to the equation of Fox from the glass transition temperatures of the homopolymers and their relative proportions).
  • n number of runs over the monomers used
  • w n mass fraction of the respective monomer n (wt .-%)
  • Ten respective glass transition temperature of the homopolymer of the respective monomers n in K.
  • equation G1 can also be used to determine and predict the glass transition temperature of polymer blends. Then, as far as homogeneous mixtures are concerned,
  • n running number over the polymers used
  • w n mass fraction of the respective polymer n (wt .-%)
  • Ten respective glass transition temperature of the polymer n in K.
  • the possible addition of tackifiers increases the glass transition temperature inevitably, depending on the addition amount, compatibility and softening temperature by about 5 to 40 K.
  • acrylate copolymers having a glass transition temperature of at most 0 ° C. are preferred.
  • the adhesive is a second, with the polyacrylate component substantially immiscible polymer elastomer-based component (hereinafter called elastomer component), in particular one or more synthetic rubbers, admixed.
  • elastomer component substantially immiscible polymer elastomer-based component
  • the adhesive preferably then comprises at least the following two components:
  • elastomer component (hereinafter called elastomer component).
  • the polyacrylate component P is present in particular at 60% by weight to 90% by weight, preferably 65% by weight to 80% by weight, and the elastomer component (E) is in particular 10 Wt .-% to 40 wt .-%, preferably 15 wt .-% to 30 wt .-% of, based on the sum of polyacrylate component (P) and elastomer component (E) as 100 wt .-%.
  • the overall composition of the adhesive may be limited in particular to these two components, but other components such as additives and the like may also be added (see also below).
  • the second polymer component (elastomer component (E)) according to the invention with the first polymer component (polyacrylate component (P)) is substantially immiscible, so that the adhesive is present in the adhesive layer in at least two separate phases.
  • one phase forms a matrix and the other phase a plurality of domains arranged in the matrix.
  • homogeneous mixtures are substances mixed at the molecular level, homogeneous systems accordingly single-phase systems.
  • the underlying substances are synonymously referred to as “homogeneously miscible,” “compatible,” and “compatible.”
  • two or more components are synonymous “non-homogeneously miscible,” “incompatible,” and “not compatible.” if, after intimate mixing, they do not form a homogeneous system but at least two phases.
  • partially homogeneously miscible As a synonym "partially homogeneously miscible”, “partially compatible”, “partially compatible” and “partially compatible” are considered components which intimately mixed together (for example by shearing, in the melt or in solution and then eliminating the solvent) at least two Forming phases that are rich in each of the components, but one or both of the phases may each have a more or less large part of the other components homogeneously mixed.
  • the polyacrylate component (P) preferably constitutes a homogeneous phase.
  • the elastomer component (E) may be homogeneous in itself, or may have in itself a multiphase, as is known from microphase-separating block copolymers. Polyacrylate and elastomer component are presently chosen so that they are - after intimate mixing - at 23 ° C (ie the usual application temperature for adhesives) are substantially immiscible.
  • substantially immiscible means that the components are either not homogeneously miscible with each other, so that none of the phases has a proportion of the second component mixed homogeneously, or that the components are only so little partially compatible - ie or both components can accommodate only such a small proportion of the other component homogeneously - that the partial compatibility is immaterial to the invention, so the teaching of the invention is not harmful.
  • the corresponding components are then considered in the sense of this document as “substantially free" of the other component.
  • the adhesive used according to the invention is present at least at room temperature (23 ° C.), in at least two-phase morphology.
  • the polyacrylate component (P) and the elastomer component (E) are substantially non-homogeneously miscible in a temperature range of from 0 ° C to 50 ° C, more preferably from -30 ° C to 80 ° C.
  • components are defined as "substantially immiscible with one another" if the formation of at least two stable phases can be physically and / or chemically detected, one phase being rich in one component-the polyacrylate component (P). and the second phase is rich in the other component - the elastomer component (E) -
  • a suitable phase separation analysis system is, for example, Scanning Electron Microscopy, but phase separation can also be seen, for example, in that the different phases contribute two independent glass transition temperatures According to the invention, phase separation is present if it can be clearly shown at least by one of the analysis methods .Phase separation can be realized in particular such that there are discrete regions (“domains") rich in one component are (formed substantially from one of the components and free from the other component) in a continuous matrix that is rich in the other component (formed essentially from the other component and free from the first component).
  • the phase separation for the adhesives used according to the invention takes place in particular such that the elastomer component (E) is dispersed in a continuous matrix of the polyacrylate component (P) (see FIG. 2).
  • the regions (domains) formed by the elastomer component (E) are preferably substantially spherical in shape.
  • the regions (domains) formed by the elastomer component (E) may also deviate from the spherical shape, in particular distorted such as elongated and oriented in the coating direction.
  • the size of the elastomer domains is in its greatest extent typically - but not necessarily - between 0.5 ⁇ and 150 ⁇ , in particular between 1 ⁇ and 30 ⁇ .
  • Other domain shapes are also possible, such as layered or rod-shaped, although these may differ in shape from ideal structures and may be bent or distorted, for example.
  • the polyacrylate component (P) and the elastomer component (E) each consist of a base polymer component, which may be a homopolymer, a copolymer or a mixture of polymers (homopolymers and / or copolymers), and optionally additives (co-components, additives).
  • a base polymer component which may be a homopolymer, a copolymer or a mixture of polymers (homopolymers and / or copolymers), and optionally additives (co-components, additives).
  • base polymer component will be referred to hereinafter as "base polymer” without the intention of excluding polymer blends for the respective base polymer component; "polyacrylate base polymer” accordingly means the base polymer component of the polyacrylate component and "elastomer base polymer” is the base polymer component of the elastomer component of the adhesive ,
  • the polyacrylate component (P) and / or the elastomer component (E) may each be present as 100% systems, that is, based solely on their respective base polymer component and without further admixture of resins, additives or the like. In a further preferred manner, one or both of these two components are mixed with other components in addition to the base polymer component, such as, for example, resins.
  • the polyacrylate component (P) and the elastomer component (E) are composed exclusively of their respective base polymer component, so that no further polymeric components are present, in particular no resins are present.
  • the entire adhesive, apart from the two base polymer components comprises no further constituents.
  • the polyacrylate-based adhesive or the polyacrylate component (P) are particularly advantageously mixed with one or more crosslinkers for a chemical and / or a physical crosslinking. Since, in principle, radiation-crosslinking of the polyacrylate component (P) is also possible, however, crosslinkers are not necessarily present.
  • Crosslinkers are those - especially bifunctional or polyfunctional, usually low molecular weight compounds - which can react under the chosen crosslinking conditions with suitable - especially functional - groups of the polymers to be crosslinked, thus two or more polymers or polymer sites link together ("bridges" form) and Thus, a cohesion of the polymer to be crosslinked or the polymers to be crosslinked to create.This usually leads to cohesion increase. The degree of crosslinking depends on the number of bridges formed.
  • crosslinker systems all crosslinker systems known to the person skilled in the art are suitable in principle for the formation of, in particular, covalent, coordinative or associative bonding systems with appropriately equipped (meth) acrylate monomers, depending on the nature of the polymers chosen and their functional groups.
  • Examples of chemical crosslinking systems are di- or polyfunctional isocyanates or di- or polyfunctional epoxides or di- or polyfunctional hydroxides or di- or polyfunctional amines or di- or polyfunctional acid anhydrides. Combinations of different crosslinkers are also conceivable.
  • crosslinkers include chelate formers which, in combination with acid functionalities in polymer chains, form complexes which act as crosslinking points.
  • the polyacrylates have functional groups with which the respective crosslinkers can react.
  • monomers for polyacrylates are acrylic acid, methacrylic acid, itaconic acid, maleic acid, fumaric acid, crotonic acid, aconitic acid, dimethylacrylic acid, ⁇ -acryloyloxypropionic acid, trichloroacrylic acid, vinylacetic acid, vinylphosphonic acid, maleic anhydride, hydroxyethyl acrylate, hydroxypropyl acrylate, hydroxyethyl methacrylate, hydroxypropyl methacrylate, 6-hydroxyhexyl methacrylate, allyl alcohol, Glycidyl acrylate, glycidyl methacrylate.
  • crosslinker 0.03 to 0.2 parts by weight, in particular 0.04 to 0.15 parts by weight of N, N, N ', N'-tetrakis (2,3-epoxypropyl) -m-xylene -a, a' diamine (tetraglycidyl-meta-xylenediamine; CAS 63738-22-7) based on 100 parts by weight of polyacrylate base polymer.
  • UV light especially if the formulation contains suitable photoinitiators or at least one polymer in the acrylate component contains comonomers with units of photoinitizing functionality
  • electron beams are suitable for this purpose.
  • the monomers used may contain functional groups which promote a subsequent radiation-chemical crosslinking.
  • Suitable copolymerizable photoinitiators are, for example, benzoin acrylate and acrylate-functionalized benzophenone derivatives.
  • Monomers which promote electron beam crosslinking are, for example, tetrahydrofurfuryl acrylate, N-he-f-butylacrylamide and allyl acrylate.
  • the PSAs are usually crosslinked, that is, the individual macromolecules are linked together by bridge bonds.
  • the networking can be done in different ways, so there are physical, chemical or thermal crosslinking methods.
  • Crosslinking of polymers is especially referred to as a reaction in which many initially linear or branched macromolecules are linked by bridge formation between the individual macromolecules to form a more or less branched network.
  • the bridging takes place in particular by suitable chemical molecules - so-called crosslinkers or crosslinking agents - react with the macromolecules, for example with certain functional groups of the macromolecules, which are particularly vulnerable to the respective crosslinking molecule.
  • cross-linker molecules can link two macromolecules together-by using one and the same cross-linker molecule with two different molecules Macromolecules reacts, ie in particular has at least two reactive centers, or crosslinking molecules can also have more than two reactive centers, so that a single crosslinker molecule can then also link together three or more macromolecules.
  • Intramolecular reactions can occur as a side reaction if one and the same crosslinker molecule attacks one and the same macromolecule with at least two of its reactive centers. In terms of effective crosslinking of the polymer, such side reactions are generally undesirable.
  • covalent crosslinkers namely those which covalently attack the macromolecules to be linked and thus form a covalent chemical bond between their corresponding reactive center and the site of attack - in particular the functional group - on the macromolecule.
  • all imaginable covalent bonds forming chemical reactions come into question.
  • coordinative crosslinkers namely those that coordinate to the macromolecules to be linked and thus form a coordinative bond between their corresponding reactive center and the site of attack - especially the functional group - on the macromolecule.
  • coordinative bonds forming chemical reactions come into question.
  • the adhesive of the layer SK1 or the layer SK2 or preferably both layers SK1 and SK2 are according to a particularly preferred embodiment of the invention - hereinafter referred to as "special embodiment" - crosslinkable adhesives, which consist in particular
  • base polymer component (hereinafter also referred to as base polymer for short) of a homopolymer, a copolymer or a homogeneous mixture of several homopolymers, several copolymers or one or more homopolymers with one or more copolymers,
  • At least one of the homopolymers or at least one of the copolymers, in particular all of the polymers of the base polymer component for the crosslinking have functional groups, (a2) optionally other components which are homogeneously miscible or soluble in the base polymer component, such as resins or additives, monomer residues, short-chain polymerization products (by-products), impurities, etc .;
  • the first base component (a) may in particular be a polyacrylate component (P) and the second component (b) in particular an elastomer component (E) in the sense of the above statements.
  • Suitable polymers for the base polymer component (a1) for the specific embodiment are in particular those polymers and polymer blends which can be crosslinked by both covalent and coordinative crosslinkers. These are in particular polymers which have free acid groups for crosslinking.
  • Acrylate copolymers can be used as preferred base polymers, in particular those polymers (copolymers, polymer blends) which are attributable to at least 50% by weight of acrylic monomers.
  • free acid groups having copolymerizable monomers are selected, more preferably, acrylic acid is used.
  • Acid group-containing monomers, such as acrylic acid have the property to influence the pressure-sensitive adhesive properties of the PSA.
  • acrylic acid is used, it is preferably used in an amount of up to at most 12.5% by weight, based on the total of the monomers of the base polymer component.
  • acrylic acid is used in an amount of up to at most 12.5% by weight, based on the total of the monomers of the base polymer component.
  • a substantially complete implementation of the crosslinker preferably at least as much acrylic acid is copolymerized in that sufficient acid groups are present are present that can lead to a substantially complete implementation of the crosslinker.
  • the polyacrylate component (a) of the advantageous PSA of the specific embodiment preferably constitutes a homogeneous phase per se.
  • the elastomer component (b) can be homogeneous in itself or can exhibit multiphase properties in itself, as is known from microphase-separating block copolymers. Polyacrylate and elastomer component are presently chosen so that they are - after intimate mixing - at 23 ° C (ie the usual application temperature for adhesives) are substantially immiscible.
  • substantially immiscible means that the components are either not homogeneously miscible with each other, so that none of the phases has a portion of the second component mixed homogeneously, or that the components are only partially compatible - so that one or both components only that the partial compatibility is insignificant for the invention, that is, the teaching according to the invention is not detrimental, the corresponding components being in the sense of this document then as "essentially free” of the respective other component considered.
  • the advantageous adhesive of the specific embodiment is present at least at room temperature (23 ° C.), in at least two-phase morphology.
  • the polyacrylate component and the elastomer component are substantially non-homogeneously miscible in a temperature range of 0 ° C to 50 ° C, more preferably still from -30 ° C to 80 ° C.
  • the polyacrylate component and / or the elastomer component can each be present as 100% systems, that is to say exclusively based on their respective polymer component ((a1) or (b1)) and without further admixture of resins, additives or the like. In a further preferred manner, one or both of these two components in addition to the base polymer component other components are added, such as resins.
  • the polyacrylate component and the elastomer component are composed exclusively of their respective polymer component ((a1) or (b1)), so that no further polymeric components are present, in particular no resins present are.
  • the polymer content of the entire adhesive, apart from the two polymer components (a1) and (b1), comprises no further constituents (without crosslinking agents in the sense of component (c) and optionally present solvents (residues) (d)).
  • the polyacrylate component (a) of the advantageous adhesive of the specific embodiment particularly comprises one or more polyacrylate-based polymers constituting the base polymer component (a1).
  • Polymers based on polyacrylates are, in particular, those polymers which are at least predominantly - in particular more than 60% by weight - due to acrylic acid esters and / or methacrylic acid, and optionally their free acids, as monomers (referred to hereinafter as "acrylic monomers") are preferably obtainable by free radical polymerization.
  • Polyacrylates may optionally contain other building blocks based on further, non-acrylic copolymerizable monomers.
  • the polyacrylates may be homopolymers and / or in particular copolymers.
  • copolymer for the purposes of this invention both those copolymers in which the comonomers used in the polymerization are purely randomly incorporated, and those in which gradients in the comonomer composition and / or local enrichments of individual comonomer types as well as whole blocks of a monomer in the polymer chains occur erende Comonomerabteil are conceivable.
  • the polyacrylates may be, for example, of linear, branched, star or grafted structure, and may be homopolymers or copolymers.
  • the average molecular weight (weight average Mw) of at least one of the polyacrylates of the polyacrylate base polymer, with several polyacrylates present advantageously the majority of weight of the polyacrylates, especially all existing Poylacrylate in the range of 250 000 g / mol to 10 000 000 g / mol, preferably in the range of 500,000 g / mol to 5,000,000 g / mol.
  • the crosslinkers of component (c) of the specific embodiment are homogeneously mixable into the base component, if appropriate after prior solution in suitable solvents.
  • covalent crosslinkers for the specific embodiment, glycidylamines are preferably used.
  • particularly preferred representatives are N, N, N ', N'-tetrakis (2,3-epoxypropyl) cyclohexane-1, 3-dimethylamine and N, N, N', N'-tetrakis (2,3-epoxypropyl) -m-xylene -a, called a'-diamine.
  • polyfunctional epoxides in particular epoxycyclohexyl carboxylates, as covalent crosslinkers.
  • polyfunctional epoxides in particular epoxycyclohexyl carboxylates
  • 2,2-bis (hydroxymethyl) -1,3-propanediol or (3,4-epoxycyclohexane) methyl 3,4-epoxycyclohexylcarboxylate is exemplified here.
  • multifunctional azeridines can be used according to the invention.
  • trimethylolpropanes tris (2-methyl-1-aziridinepropionate) may be mentioned for this purpose.
  • isocyanates in particular polyfunctional isocyanate compounds.
  • multifunctional isocyanate compound for example, tolylene diisocyanate (TDI), 2,4-Tolylendiisocyanatdimer, naphthylene-1, 5-diisocyanate (NDI), o-tolylene diisocyanate (TODI), diphenylmethane diisocyanate (MDI), triphenylmethane triisocyanate, tris (p-isocyanatophenyl) thiophos- phit, polymethylene polyphenyl isocyanate can be used. They may be used alone or in a combination of two or more kinds thereof.
  • At least one covalent crosslinker is used according to the invention, but it is also possible to use two or more covalent crosslinkers, for example the two abovementioned diamine compounds in combination with one another.
  • Suitable coordinative crosslinkers (component (c2)) for the specific embodiment are, in particular, chelate compounds, in particular polyvalent metal chelate compounds.
  • chelate compounds in particular polyvalent metal chelate compounds.
  • polyvalent metal chelate compound is meant those compounds in which a polyvalent metal is coordinately bonded to one or more organic compounds.
  • ligands of the coordinative crosslinkers of the specific embodiment basically all known ligands can use these.
  • the atoms used for the coordinate binding of the organic compound can be, in particular, those which have electron pairs, such as, for example, oxygen atoms, sulfur atoms, Nitrogen atoms and the like.
  • the organic compound for example, alkyl esters, alcohol compounds, carboxylic acid compounds, ether compounds, ketone compounds and the like can be used. In particular, be
  • Titanium chelate compounds such as titanium dipropoxide bis (acetylacetonate), titanium dibutoxide bis (octylene glycolate), titanium dipropoxide bis (ethylacetoacetate), titanium dipropoxide bis (lactate), titanium dipropoxide bis (triethanolaminate), titanium di-n-butoxide bis (triethanolaminate), titanium tri-n-butoxide monostearate, butyl titanate dimer,
  • Aluminum chelate compounds such as aluminum diisopropoxide monoethyl acetate, aluminum di-n-butoxide monomethylacetoacetate, aluminum di-i-butoxide monomethylacetoacetate, aluminum di-n-butoxide monoethyl acetoacetate, aluminum disec-butoxide monoethylacetoacetate, aluminum triacetylacetonate, aluminum triethylacetoacetonate, aluminum monoacetylacetonatebis (ethylacetoacetonate) and the like, and zirconium chelate compounds such as zirconium tetraacetylacetonate and the like.
  • aluminum triacetylacetonate and aluminum dipropoxide are preferred. They may be used alone or in a combination of two or more kinds thereof.
  • Covalent crosslinkers (c1) are preferably used in the specific embodiment in a total amount of 0.015 to 0.04, preferably 0.02 to 0.035 parts by weight, based on 100 parts by weight of the base polymer component (a1), more preferably in an amount of 0.03 wt .%.
  • Coordinative crosslinkers (c2) in the specific embodiment are preferably used in an amount of 0.03 to 0.15, preferably 0.04 to 0.1 part by weight based on 100 parts by weight of the base polymer component (a1).
  • covalent crosslinkers and coordinating crosslinkers are used in the specific embodiment such that the coordinative crosslinkers are present in molar excess, based on the covalent crosslinkers.
  • the crosslinkers are preferably used in the abovementioned amounts ranges, in such a way that the molar ratio of covalent crosslinkers to coordinative crosslinkers - ie the ratio of the amount of substance used n ⁇ the covalent crosslinker to the amount used nkoord the coordinative crosslinkers - in the range of 1 : 1, 3 to 1: 4,5, corresponding to 1, 3 ⁇ nkoord nkov ⁇ 4,5.
  • Very preferred is a molar ratio of covalent crosslinkers to coordinating crosslinkers of 1: 2 to 1: 4. Elastomer component of the adhesive used according to the invention, in particular of the specific embodiment
  • the adhesive used according to the invention may comprise substantially non-homogeneously miscible polymers with the polyacrylate component or the base polymer, in particular an elastomer component.
  • the elastomer component which is substantially incompatible with the polyacrylate component in turn advantageously comprises one or more than one independently chosen synthetic rubber as the base polymer component.
  • the synthetic rubber used is preferably at least one vinylaromatic block copolymer in the form of a block copolymer having a structure AB, ABA, (AB) n , (AB) n X or (ABA) n X, ABX (A'-B ') n
  • the blocks B and B 'independently represent a polymer formed by polymerization of conjugated dienes having 4 to 18 carbon atoms and / or a polymer of an isoprene, butadiene, a Farnesen isomer or a
  • - n stands for an integer> 2.
  • all synthetic rubbers are block copolymers having a structure as set forth above.
  • the synthetic rubber may thus also contain mixtures of various block copolymers having a structure as above.
  • Suitable block copolymers (vinylaromatic block copolymers) thus comprise one or more rubbery blocks B or B '(soft blocks) and one or more glassy blocks A or A' (hard blocks).
  • Particularly preferred is a block copolymer having a structure AB, ABA, (AB) sX or (AB) 4 X, where A, B and X are as defined above.
  • the synthetic rubber is a mixture of block copolymers having a structure AB, ABA, (A-B) 3X or (AB) 4X, which preferably contains at least diblock copolymers AB and / or triblock copolymers ABA.
  • a block copolymer which is a multi-arm block copolymer is additionally or exclusively used. This is by the general formula
  • each arm Q independently has the formula A * -B * , where A * and B * are each selected independently of the remaining arms in accordance with the above definitions for A and A and B and B ', respectively, such that each A * is a glassy block and B * represents a soft block.
  • a * and / or identical B * for several arms Q or all arms Q.
  • the blocks A, A 'and A * will hereinafter be referred to collectively as A-blocks.
  • the blocks B, B 'and B * are hereinafter referred to collectively as B-blocks.
  • a blocks are generally glassy blocks each having a glass transition temperature above room temperature (below room temperature, in the context of this invention, being 23 ° C).
  • the glass transition temperature of the glassy block is at least 40 ° C, preferably at least 60 ° C, more preferably at least 80 ° C, or most preferably at least 100 ° C.
  • the vinyl aromatic block copolymer further generally has one or more rubbery B blocks having a glass transition temperature less than room temperature on.
  • the Tg of the soft block is less than -30 ° C or even less than -60 ° C.
  • further advantageous embodiments comprise a polymerized conjugated diene, a hydrogenated derivative of a polymerized conjugated diene or a combination thereof.
  • the conjugated dienes comprise 4 to 18 carbon atoms.
  • Preferred conjugated dienes as monomers for soft block B are in particular selected from the group consisting of butadiene, isoprene, ethylbutadiene, phenylbutadiene, piperylene, pentadiene, hexadiene, ethylhexadiene and dimethylbutadiene and also any desired mixtures of these monomers.
  • Block B can also be present as a homopolymer or as a copolymer.
  • ethylbutadiene, phenylbutadiene, piperylene, pentadiene, hexadiene, ethylhexadiene and dimethylbutadiene may additionally be mentioned for further advantageous conjugated dienes for the B blocks, it being possible for the polymerized conjugated dienes to be present as homopolymer or as copolymer.
  • the conjugated dienes are particularly preferred as monomers for the soft block B selected from butadiene and isoprene.
  • the soft block B is a polyisoprene, a polybutadiene or a partially or fully hydrogenated derivative of one of these two polymers, in particular polybutylene-butadiene; or a polymer of a mixture of butadiene and isoprene.
  • the block B is a polybutadiene.
  • the proportion of A blocks based on the total block copolymers is on average preferably 10 to 40 wt .-%, more preferably 15 to 33 wt .-%.
  • Preferred as a polymer for A blocks is polystyrene.
  • Preferred polymers for B blocks are polybutadiene, polyisoprene, polyarnarnes and their partially or fully hydrogenated derivatives such as polyethylene butylene, polyethylene propylene, polyethylene ethylenepropylene or polybutylene butadiene or polyisobutylene. Very preferred is polybutadiene.
  • Block copolymers can be linear, radial or star-shaped (multiarm).
  • the adhesives used in accordance with the invention may in particular be resin-free, since the polyacrylate component itself often already has pressure-sensitive tackiness and the pressure-sensitive adhesive character is retained even when the elastomer component is present. Nevertheless, it may be of interest to further improve the adhesive properties or to optimize them for special applications, therefore adhesives can be added to the adhesives in an advantageous further development of the invention.
  • tackifiers also referred to as tackifier resins
  • the self-adhesive acrylate composition 15 to 100 parts by weight of tackifiers (based on the polymers, ie acrylates plus optionally elastomers such as synthetic rubbers) is added, usually 20 to 80 parts by weight, more preferably 30 to 50 parts by weight.
  • an "adhesive resin” is understood as meaning an oligomeric or polymeric resin which increases the autoadhesion (tack, inherent tack) of the pressure-sensitive adhesive in comparison with the otherwise non-adhesive-containing, otherwise identical pressure-sensitive adhesive
  • Tackifiers are, for example, nonhydrogenated, partially, selectively or completely hydrogenated hydrocarbon resins (for example polymers based on unsaturated Cs, C5 / C9 or Cg monomers), terpene-phenolic resins, polyterpene resins based on raw materials such as a-, beta - Pinen and / or or ⁇ -limonene, aromatic resins such as coumarone-indene resins or resins based on styrene or ⁇ -methylstyrene such as rosin and its derivatives, for example disproportionated, dimerized or esterified rosin, for example reaction products with glycol, glycerol or Pentaeryth
  • resins without easily oxidizable double bonds such as terpene-phenolic resins, aromatic resins and particularly preferably resins which are prepared by hydrogenation such as hydrogenated aromatic resins, hydrogenated polycyclopentadiene resins, hydrogenated rosin derivatives or hydrogenated polyterpene resins.
  • resins based on terpene phenols and rosin esters Preference is given to resins based on terpene phenols and rosin esters. Also preferred are tackifier resins having a softening point above 80 ° C according to ASTM E28-99 (2009). Particular preference is given to resins based on terpene phenols and rosin esters having a softening point above 90 ° C. according to ASTM E28-99 (2009).
  • the adhesive formulation may optionally be blended with sunscreen or primary and / or secondary anti-aging agents.
  • products based on sterically hindered phenols, phosphites, thiosynergists, sterically hindered amines or UV absorbers can be used.
  • primary antioxidants such as Irganox 1010 or Irganox 254, alone or in combination with secondary antioxidants such as Irgafos TNPP or Irgafos 168.
  • the anti-aging agents can be used in any combination with each other, with mixtures of primary and secondary antioxidants in combination with light stabilizers such as Tinuvin 213 show particularly good aging protection.
  • Anti-aging agents have proven particularly advantageous in which a primary antioxidant is combined with a secondary antioxidant in one molecule.
  • These antioxidants are cresol derivatives whose aromatic ring is substituted with thioalkyl chains at any two different positions, preferably in the ortho and meta position relative to the OH group, the sulfur atom also having one or more alkyl chains on the aromatic ring of the cresol component can be connected.
  • the number of carbon atoms between the aromatic and the sulfur atom may be between 1 and 10, preferably between 1 and 4.
  • the number of carbon atoms of the alkyl side chain may be between 1 and 25, preferably between 6 and 16.
  • the amount of the aging protection agent or aging protection agent package added should be in a range between 0.1 and 10 parts by weight, preferably in a range between 0.2 and 5 parts by weight, more preferably in a range between 0.5 and 3 wt.
  • Parts based on the polymer content acrylates plus optionally elastomers such as synthetic rubbers.
  • the formulation may also be blended with conventional process auxiliaries, such as rheology additives (thickeners), defoamers, deaerators, wetting agents or leveling agents. Suitable concentrations are in the range of 0.1 to 5 parts by weight based on the polymer content (acrylates plus optionally elastomers such as synthetic rubbers).
  • Fillers such as silicas (spherical, acicular, platy or irregular, such as pyrogenic silicas), calcium carbonates, zinc oxides, titanium dioxides, aluminum oxides or aluminum oxide hydroxides, can serve both to adjust the processability and the adhesive properties. Suitable concentrations are in the range from 0.1 to 20 parts by weight, based on the polymer content (acrylates plus optionally elastomers, such as synthetic rubbers).
  • the self-adhesive acrylate composition which forms the layers SK1 and / or SK2 comprises, according to a preferred embodiment of the invention, a polymer mixture of acrylates and synthetic rubbers, wherein one or more crosslinkers and tackifiers are admixed with the polymer mixture.
  • the layer SK1 or the layer SK2 or preferably both layers SK1 and SK2 contain a black pigment such as carbon black.
  • the proportion is particularly preferably 0.1 part by weight and 10 parts by weight, based on the total composition of the particular layer. Foaming and design of the self-adhesive acrylate compound layers
  • the layers SK1 and SK2 are foamed.
  • the foam is obtained by the introduction and subsequent expansion of microballoons.
  • microballoons is understood as meaning elastic hollow microspheres which are expandable in their ground state and which have a thermoplastic polymer shell These spheres are filled with low-boiling liquids or liquefied gas Hydrocarbons of the lower alkanes, for example isobutane or isopentane, which are enclosed as liquefied gas under pressure in the polymer shell
  • Low-boiling liquids or liquefied gas Hydrocarbons of the lower alkanes for example isobutane or isopentane
  • the liquid propellant gas contained in the shell goes into
  • the microballoons expand irreversibly and expand three-dimensionally.The expansion is completed when the internal and external pressures equalize, as the polymeric shell remains intact t, one achieves such a closed-cell foam.
  • microballoons there are a variety of types of microballoons available commercially, which differ essentially by their size (6 to 45 ⁇ diameter in the unexpanded state) and their expansion required for starting temperatures (75 to 220 ° C).
  • Unexpanded microballoon types are also available as an aqueous dispersion having a solids or microballoon content of about 40 to 45 wt%, and also as polymer bound microballoons (masterbatches), for example in ethyl vinyl acetate having a microballoon concentration of about 65 wt%. Both the microballoon dispersions and the masterbatches, like the DU types, are suitable for producing a foamed PSA according to the invention.
  • Foamed layers SK1 and SK2 can also be produced with so-called pre-expanded microballoons.
  • one of the layers SK1 or SK2 or both layers SK1 and SK2 may be foamed in this way.
  • pre-expanded microballoons an expansion takes place even before the mixing into the polymer matrix.
  • Pre-expanded microballoons are commercially available, for example under the designation Dualite ® or with the type designation Expancel DE xxx yy (Dry Expanded) from Akzo Nobel.
  • "xxx" represents the composition of the microballoon blend
  • yy represents the size of the microballoons in the expanded state.
  • microballoons When processing already expanded types of microballoons, it may happen that the microballoons, due to their low density in the polymer matrix into which they are to be incorporated, tend to float, ie "float upwards" in the polymer matrix during the processing process Uneven distribution of the microballoons in the layer More microballoons are found in the upper area of the layer (z-direction) than in the lower area of the layer, so that a density gradient is established over the layer thickness.
  • FIG. is a gradient in the distribution of microballoons.
  • In the upper part of the foam layer are more and especially more expanded microballoons than in the lower part of the foam layer.
  • microballoons are incorporated into the polymer matrix of the layer SK1 or the layer SK2 or preferably both layers SK1 and SK2. Only after incorporation into the layer are the microballoons expanded. This results in a more uniform distribution of the microballoons in the polymer matrix (see FIG. 3). It can be seen in FIG. 3 that microballoons expanded uniformly are present both in the upper and in the lower region of the foam layer. The degree of expansion of the microballoons is also more balanced overall. Almost all microballoons are expanding at the same time.
  • the microballoons are selected such that the ratio of the density of the polymer matrix to the density of the (not or only slightly pre-expanded) microballoons to be incorporated into the polymer matrix is between 1 and 1: 6, ie: Density of the polymer matrix
  • the microballoons are preferably expanded only after incorporation, coating, drying (solvent evaporation).
  • DU types are therefore preferably used according to the invention.
  • At least 90% of all cavities formed by microballoons in the layer SK1 or the layer SK2 or preferably both streams SK1 and SK2 have a maximum diameter of from 7 to 200 ⁇ m, more preferably from 10 to 100 ⁇ m, very particularly preferably from 10 to 30 ⁇ on.
  • maximum diameter is understood to mean the maximum extent of a microballoon in any desired spatial direction.
  • the size of the elastomer domains lies in their greatest extent typically between 0, 5 ⁇ and 150 ⁇ , especially between 1 ⁇ and 30 ⁇ , see above, most preferably the maximum diameter of at least 90% of all cavities formed by microballoons and the maximum diameter of at least 90% of the domains of the elastomer component are in the same Size range below 100 ⁇ , in each case in the range between 10 ⁇ and 30 ⁇ .
  • the determination of the diameter is based on a Kryobruch edge in the scanning electron microscope (SEM) at 500-fold magnification. From each individual microballoon, the diameter is determined graphically.
  • microballoons can be fed to the formulation as a batch, paste or as uncut or blended powder. Furthermore, they may be suspended in solvent.
  • the proportion of the microballoons in the layer SK1 or the layer SK2 or preferably both layers SK1 and SK2 is according to a preferred embodiment of the invention between greater than 0 wt .-% and 12 wt .-%, in particular between 0.25%. Parts and 5 wt .-%, more preferably between 0.5 and 3 wt .-%, each based on the total composition (including blended microballoons) of the corresponding layer SK1 or SK2.
  • the data refer to unexpanded microballoons.
  • An expandable hollow microspheres containing polymer composition of the layer SK1 or the layer SK2 or both layers SK1 and SK2 may also contain non-expandable hollow microspheres.
  • the decisive factor is that almost all caverns containing gas are closed by a permanently sealed membrane, regardless of whether this membrane consists of an elastic and thermoplastic polymer mixture or of elastic and non-thermoplastic glass in the range of possible temperatures in plastics processing ,
  • layers SK1 and SK2 are polymer full spheres, such as PMMA spheres, glass hollow spheres, glass solid spheres, phenolic resin spheres, ceramic hollow spheres, ceramic solid spheres and / or carbon full spheres, independently of other additives, including the additives mentioned here can either be present only in one of the layers SK1 or SK2 or in both layers SK1 and SK2.
  • polymer full spheres such as PMMA spheres, glass hollow spheres, glass solid spheres, phenolic resin spheres, ceramic hollow spheres, ceramic solid spheres and / or carbon full spheres, independently of other additives, including the additives mentioned here can either be present only in one of the layers SK1 or SK2 or in both layers SK1 and SK2.
  • the absolute density of the foamed layer SK1 or the layer SK2 or preferably both layers SK1 and SK2 is preferably 350 to 950 kg / m 3 , more preferably 450 to 930 kg / m 3 , in particular 570 to 880 kg / m 3 .
  • the relative density describes the ratio of the density of each foamed layer to the density of the corresponding formulation-identical unfoamed layer.
  • the specific gravity of the layer SK1 or the layer SK2 or preferably both layers SK1 and SK2 is preferably 0.35 to 0.99, more preferably 0.45 to 0.97, especially 0.50 to 0.90.
  • non-stretchable - film carrier F preferably polyester, in particular polyethylene terephthalate (PET), polyamide (PA), polyimide (PI) or mono- or biaxially stretched polypropylene (PP) are used. Also possible is also the use of multilayer laminates or coextrudates, in particular of the aforementioned materials.
  • the film carrier is single-layered.
  • one of the surfaces or surfaces of the film support layer is physically / and / or chemically pretreated, for example by etching and / or corona treatment and / or plasma treatment and / or priming.
  • reagent for etching the film trichloroacetic acid (C C -COOH) or trichloroacetic acid in combination with inert crystalline compounds, preferably silicon compounds, particularly preferably [SiO 2] x.
  • the purpose of the inert crystalline compounds is to be incorporated in the surface of the film, in particular the PET film, in order to increase the roughness and surface energy in this way.
  • Corona treatment is a chemical-thermal process for increasing the surface tension / surface energy of polymeric substrates. Between two electrodes, electrons are strongly accelerated in a high-voltage discharge, which leads to an ionization of the air. When a plastic substrate is introduced into the path of these accelerated electrodes, the accelerated electrodes thus produced strike the substrate surface at 2 to 3 times the energy needed to superficially disrupt the molecular bonds of most of the substrates. This leads to the formation of gaseous reaction products and highly reactive, free radicals. These free radicals can react rapidly in the presence of oxygen and the reaction products to form various chemical functional groups on the substrate surface. Functional groups resulting from these oxidation reactions contribute most to increasing the surface energy.
  • the corona treatment can be done with two-electrode, but also with single-electrode systems.
  • corona pretreatment During corona pretreatment, different process gases, such as nitrogen, can be used (in addition to conventional air) to form a protective gas atmosphere or support corona pretreatment.
  • the plasma treatment - in particular low-pressure plasma treatment - is a known method for the surface pretreatment of adhesives.
  • the plasma leads to an activation of the surface in the sense of a higher reactivity. This leads to chemical changes of the surface, whereby for example the behavior of the adhesive against polar and non-polar surfaces can be influenced.
  • This pretreatment is essentially surface phenomena.
  • Coatings or primers are generally referred to as primers which in particular have adhesion-promoting and / or passivating and / or corrosion-inhibiting effects.
  • the adhesion-promoting effect is particularly important.
  • Adhesion-promoting primers often also referred to as adhesion promoters or adhesion promoters, are widely known in the form of commercial products or from the technical literature.
  • the thickness of the film is according to a preferred embodiment, between 5 and 250 ⁇ , preferably between 6 and 120 ⁇ , in particular between 12 and 100 ⁇ , especially between 23 and 50 ⁇ .
  • the film consists of polyethylene terephthalate and has a thickness between 23 and 50 ⁇ .
  • a suitable film is available under the trade name Hostaphan® RNK.
  • This film is highly transparent, biaxially oriented and consists of three coextruded layers.
  • additives and other components which improve the film-forming properties, reduce the tendency to form crystalline segments and / or specifically improve or even worsen the mechanical properties.
  • films which meet the following values for tensile strength and / or elongation at break are considered to be inextensible for the purposes of the present application.
  • the tensile strength of the film is in the longitudinal and in the transverse direction in each case preferably greater than 100 N / mm 2 , preferably greater than 150 N / mm 2 . Most preferably, the tensile strength of the film is greater than 100 N / mm 2 , more preferably greater than 180 N / mm 2 (in the longitudinal direction) and greater than 200 N / mm 2 , more preferably greater than 270 N / mm 2 (in the transverse direction).
  • the elongation at break of the film is preferably less than 300%, preferably less than 200% (in the longitudinal direction) and less than 300%, preferably less than 120% (in the transverse direction), these values being able to be realized independently of those stated for the tensile strength or simultaneously.
  • the film significantly determines the tensile strength or elongation at break of the pressure-sensitive adhesive strip.
  • the pressure-sensitive adhesive strip has the same values of tensile strength and elongation at break as stated above.
  • the preparation and processing of the pressure-sensitive adhesives can be carried out both from the solution and from the melt.
  • the application of the PSAs may be effected by direct coating or by lamination, in particular hot lamination.
  • the thickness of the self-adhesive mass layers SK1 and SK2 is preferably between 10 and 500 ⁇ m in each case.
  • the outer, exposed surfaces of the outer adhesive layers SK1 and / or SK2 of the pressure-sensitive adhesive strip according to the invention can be equipped with materials coated on both sides with anti-adhesive coating, such as a release paper or a release film, also called a liner, as a temporary carrier.
  • anti-adhesive coating such as a release paper or a release film, also called a liner
  • a liner (release paper, release film) is not part of an adhesive tape, but only an aid for its production, storage and / or for further processing by punching.
  • a liner is not firmly bonded to an adhesive layer.
  • Typical preforming forms of the pressure-sensitive adhesive strips according to the invention are adhesive tape rolls and adhesive strips, as obtained, for example, in the form of diecuts.
  • all layers have substantially the shape of a cuboid.
  • all layers are connected to each other over the entire surface. This compound can be optimized by pretreating the film surfaces.
  • the general term "adhesive strips”, also synonymously “adhesive tape”, in the sense of this invention encompasses all planar structures such as films or film sections expanded in two dimensions, belts of extended length and limited width, belt sections and the like, ultimately Diecuts or labels.
  • the pressure-sensitive adhesive strip thus has a longitudinal extent (x-direction) and a width extent (y-direction).
  • the pressure-sensitive adhesive strip also has a thickness extending perpendicularly to the two dimensions (z-direction), the width dimension and longitudinal extent being many times greater than the thickness. The thickness over the entire length and width determined surface extent of the pressure-sensitive adhesive strip as equal as possible, preferably exactly the same.
  • the pressure-sensitive adhesive strip according to the invention is in particular in web form.
  • Under a track is understood to be an object whose length (extension in the x direction) is greater by a multiple than the width (extension in the y direction) and the width along the entire length in approximately preferably exactly the same formed.
  • the pressure-sensitive adhesive strip in particular in the form of a web, can be produced in the form of a roll, ie in the form of an Archimedean spiral wound on itself.
  • the three-layer pressure-sensitive adhesive strip (that is, without taking into account possibly provided liners) preferably has a thickness of from 20 ⁇ m to 6,000 ⁇ m, more preferably from 30 to 500 ⁇ m, particularly preferably from 45 to 350 ⁇ m.
  • the layer SK1 of a self-adhesive mass or the layer SK2 of a self-adhesive mass or preferably both layers SK1 and SK2 are very preferably crosslinked in the pressure-sensitive adhesive strip according to the invention.
  • the crosslinking preferably takes place on the layer or film of the pressure-sensitive adhesive.
  • the crosslinking reaction can take place in particular as follows:
  • the two substances are pre-dissolved as pure substance or in a suitable solvent to the polymer present in solution, then the polymer thoroughly mixed with the crosslinkers, coated on a temporary or permanent support and then dried under suitable conditions, wherein the crosslinking takes place.
  • first of all one of the crosslinkers is added in pure form or pre-dissolved to the polymer solution.
  • the second crosslinker is supplied shortly before the coating, for example via an in-line metering with a downstream active or static mixer and subsequent coating and drying.
  • the pot life (processing time) of the coordinative crosslinkers can be increased by adding the previously described ligands to the polymer crosslinker solution. The excess ligand is then removed on drying; only then are the coordinative crosslinkers (fully) reactive.
  • the drying conditions are very preferably chosen so that not only the solvent is removed, but also the crosslinking is completed to a large extent, so that a stable level of crosslinking - especially at higher temperatures - is achieved.
  • the adhesive is completely crosslinked.
  • Complete crosslinking of an adhesive is understood in accordance with the invention to mean that its maximum shear distance "max" in the micro-shear test under the conditions specified therein for repeated (for example daily) micro-shear path measurement within a period of 48 hours only within the accuracy of the measurement method (approximately to to a maximum of 5%) changes when the adhesive is stored at room temperature (23 ° C) under otherwise normal conditions.
  • the detection of complete crosslinking can also be carried out for other temperatures (for example 40 ° C., in particular those temperatures which correspond to the respective application temperatures).
  • the pressure-sensitive adhesive strip according to the invention can be used for bonding components of precision mechanical, optical, electrical and / or electronic devices, for example during their manufacture, repair, decoration or the like. In this case, for example, materials such as plastics, glasses, metals and the like come for bonding.
  • the pressure-sensitive adhesive strip according to the invention is also particularly suitable for the permanent bonding of flexible materials, in particular in the manufacture of flexible displays. Such displays are becoming more important.
  • the pressure-sensitive adhesive strip according to the invention can be used for bonding windows or lenses in housings of precision mechanical, optical and / or electronic devices (so-called “lens mounting"), whereby at least one of the rigid or flexible substrates is transparent (transparent) or translucent (translucent)
  • the transparent substrate may be a window or an optical lens for the purpose of protecting sensitive components disposed thereunder such as liquid crystal displays (LCDs), light emitting diodes (LEDs) or organic light emitting diodes (OLEDs) of displays, but also printed circuits or other sensitive electronic components, for example, plays an important role in the application for touch-sensitive displays - and / or for effecting optical effects for the function of the device - for example refraction of light, light bundling, Lichta weakening, light amplification, etc. - be.
  • LCDs liquid crystal displays
  • LEDs light emitting diodes
  • OLEDs organic light emitting diodes
  • the transparent substrate is selected such that it has a haze value of at most 50%, preferably not more than 10%, very preferably not more than 5% (measured according to ASTM D 1003).
  • the second substrate is preferably also a component of a precision mechanical, optical and / or electronic device.
  • here is to think of housing such devices or brackets for windows or lenses as described above.
  • the transparent or translucent substrate is a substrate of glass, polymethyl methacrylate and / or polycarbonate.
  • the second substrate made of plastics such as acrylonitrile-butadiene-styrene copolymers (ABS), polyamide or polycarbonate, in particular also can be glass fiber reinforced; or of metals, such as aluminum - also anodized (anodized) aluminum - or magnesium and metal alloys
  • ABS acrylonitrile-butadiene-styrene copolymers
  • polyamide or polycarbonate in particular also can be glass fiber reinforced; or of metals, such as aluminum - also anodized (anodized) aluminum - or magnesium and metal alloys
  • the substrate materials may be blended with additives such as dyes, light stabilizers, anti-aging agents, plasticizers or the like, if advantageous for the intended purpose; in the case of transparent or translucent materials, in particular in so far as it does not or only to a reasonable extent disturb these optical properties.
  • the composite according to the invention is thus a component of an electronic, optical or precision mechanical device, as indicated in the table above.
  • FIG. 1 shows the schematic structure of a three-layer pressure-sensitive adhesive strip according to the invention comprising three layers 1, 2, 3 as a cross section.
  • the strip comprises a non-stretchable film carrier 1 (layer F) in the form of a double-sided etched PET film.
  • the self-adhesive adhesive layers 2, 3 are in turn covered in the illustrated exemplary embodiment in each case with a liner 4, 5.
  • the adhesive In a production process according to the invention, all constituents of the adhesive are dissolved in a solvent mixture (gasoline / toluene / acetone).
  • the microballoons were slurried in gasoline and stirred into the dissolved adhesive.
  • the known compounding and stirring units can be used, it being important to ensure that the microballoons do not expand during mixing.
  • the adhesive can be coated, again using coating systems according to the prior art. For example, the coating done by a squeegee on a conventional PET liner.
  • the adhesive layer thus prepared is dried at 100 ° C for 15 min.
  • the non-stretchable film layer F is laminated on the free surface of the adhesive layer thus prepared and dried.
  • the second surface of the free surface of a second thus prepared also dried adhesive layer is laminated, so that a non-foamed three-layer composite of the inner film layer and two provided with liners adhesive layers results.
  • the film layer F can be coated directly or simultaneously with the non-foamed adhesives provided with microballoons, whereupon these still exposed adhesive layers are dried at 100 ° C. for 15 minutes and then covered with liners, so that the unfoamed three-layer composite results. After drying, the adhesive layers are oven-foamed in an appropriate temperature-time window, for about 5 minutes at 150 ° C or for 1 minute at 170 ° C, covered between the two liners to provide a particularly smooth surface produce.
  • the surface thus produced has a roughness R a of less than 15 ⁇ m, particularly preferably less than 10 ⁇ m, very particularly preferably of less than 3 ⁇ m.
  • the surface roughness is preferably R a is an industry standard unit for surface finish quality and represents the average height of the roughness, in particular the average absolute distance from the centerline of the roughness profile within the evaluation range. This is measured by means of laser triangulation.
  • the expansion temperature is chosen to be higher than the drying temperature in order to avoid expansion of the microballoons during drying.
  • the pressure-sensitive adhesive strips according to the invention are distinguished by an outstanding application profile which excellently fulfills the requirements of the problem set according to the invention. It has been found that in particular the Shock absorption capacity is better than in the products of the prior art, in particular also with regard to equally thick four-layer products of PET carrier, foamed inner layer and outer PSA layers. The invention will be explained in more detail by some examples.
  • the preparation of the starting polymer and the blends with microballoons produced therefrom are described below.
  • the investigated polymers are conventionally prepared by free radical polymerization in solution.
  • a reactor conventional for radical polymerizations was charged with 47.5 kg of 2-ethylhexyl acrylate, 47.5 kg of n-butyl acrylate, 5 kg of acrylic acid and 66 kg of gasoline / acetone (70/30). After passage of nitrogen gas for 45 minutes with stirring, the reactor was heated to 58 ° C and 50 g of AIBN was added. Subsequently, the outer heating bath was heated to 75 ° C and the reaction was carried out constantly at this external temperature. After 1 h, 50 g of AIBN were again added and after 4 h was diluted with 20 kg of gasoline / acetone mixture.
  • a mixture comprising 42.425% by weight, based on the dry weight of the polymer, of the base polymer P1, 37.5% by weight of the resin Dertophene T and 20% by weight of Kraton D 1 1 18.
  • Gasoline becomes a solid content set by 38%.
  • the mixture of polymer and resin is stirred until the resin has visibly dissolved completely. This is followed by 0.075% by weight of the covalent crosslinker Erysis GA 240 (N, N, N ', N'-tetrakis (2,3-epoxypropyl) -m-xylene- ⁇ , ⁇ '-diamine from Emerald Performance Materials, CAS NO 63738-22-7).
  • the mixture is stirred for 15 minutes at room temperature.
  • a mixture is prepared comprising 42.34 wt .-%, based on the dry weight of the polymer, the base polymer P1, 35.25 wt .-% of the resin Dertophene T and 17 wt .-% Kraton D 1 1 18.
  • gasoline is adjusted to a solids content of 38%.
  • the mixture of polymer and resin is stirred until the resin has visibly dissolved completely.
  • 0.035% by weight of the covalent crosslinker Erysis GA 240 (a tetrafunctional epoxy resin based on meta-xylenediamine, CAS NO 63738-22-7) and 0.075% by weight of Al chelate are added. The mixture is stirred for 15 minutes at room temperature.
  • a mixture comprising 29.925% by weight, based on the dry weight of the polymer, of the base polymer P1, 30% by weight of the Dertophene T resin and 40% by weight of Kraton D11 -18 by the addition of gasoline a solids content of 38% is set.
  • the mixture of polymer and resin is stirred until the resin has visibly dissolved completely.
  • 0.075% by weight of the covalent crosslinker Erysis GA 240 (a tetrafunctional epoxy resin based on meta-xylenediamine, CAS NO. 63738-22-7) is added. The mixture is stirred for 15 minutes at room temperature.
  • Example of Adhesive Adhesive B4 A mixture is prepared comprising 42.34% by weight, based on the dry weight of the polymer, of the base polymer P1, 35.25% by weight of the resin Dertophene T and 17% by weight of Kraton D11 18. The addition of gasoline sets a solids content of 38%. The mixture of polymer and resin is stirred until the resin has visibly dissolved completely.
  • Al chelate Al- (III) acetylacetonate (Sigma Aldrich)
  • the respective blends for producing the microballoon-containing layer are coated with the desired basis weight (see Table 3) on a process liner (siliconized film).
  • the layers thus obtained are dried (100 ° C. for 15 minutes) and used as layers SK1 and SK2 for the pressure-sensitive adhesive tapes.
  • Three-layered symmetrical pressure-sensitive adhesive tapes (Examples 1 to 28, Comparative Examples 3 and 4) are obtained by laminating the respective layers SK1 and SK2, which are still unfoamed on the process liner, with their respective exposed pressure-sensitive adhesive surfaces to the two pretreated surfaces of a PET film (Pretreatment of the surfaces as indicated in Table 3, where "corona” stands for the corona pretreatment)).
  • Comparative 4-layer adhesive tapes (Comparative Examples 1 and 2) are obtained by laminating a dried, microballoon-containing adhesive layer (as shown in Table 3) with its free pressure-sensitive adhesive surface onto a PET film etched on both sides. Thereafter, a layer of the external pressure-sensitive adhesives present on a process liner and optionally dried is laminated to the outer surfaces of the composite of PET film and microballoon-containing layer thus obtained.
  • the last step of the respective adhesive strip production involves the foaming of the layers of the respective pressure-sensitive adhesive strip to be foamed by the action of warm air (about 170 ° C.) for about one minute.
  • one or both of the outer liners for the examinations are removed again.
  • Example 3 54 g / m 2 blend 3 150 mm
  • Example 6 54 g / m 2 mixture 5 150 mm
  • Example 7 38 g / m 2 mixture 5 1 10 mm
  • Example 8 33 g / m 2 mixture 6 1 10 mm
  • Example 9 30 g / m 2 mixture 7 1 10 mm
  • Example 1 1 94 g / m 2 mixture 1 300 mm
  • Example 20 100 g / m 2 mixture 4 300 mm
  • Example 21 40 g / m 2 mixture 3 100 mm
  • Example 22 36 g / m 2 mixture 9 100 mm
  • Example 23 30 g / m 2 mixture 1 100 mm
  • Example 24 27 g / m 2 mixture 10 100 mm
  • Example 25 40 g / m 2 mixture 1 1 100 ⁇
  • Example 26 36 g / m 2 mixture 12 100 ⁇
  • Example 27 30 g / m 2 mixture 13 100 ⁇
  • Example 28 27 g / m 2 mixture 14 100 ⁇
  • Comparative Example 1 30 g / m 2 pressure-sensitive adhesive 2 * 150 ⁇
  • Comparative Example 2 75 g / m 2 adhesive 2 * 300 ⁇
  • the elongation at break and the tensile strength were measured in accordance with DIN 53504 using S3 size shoulder bars at a separation rate of 300 mm per minute.
  • the test climate was 23 ° C and 50% rel. Humidity.
  • Adhesive resin softening temperature (method R2)
  • the adhesive resin softening temperature is carried out according to the relevant methodology known as Ring & Ball and standardized according to ASTM E28.
  • the data on the number average molecular weight Mn, the weight average molecular weight Mw and the polydispersity PD refer to the determination by gel permeation chromatography. The determination is carried out on 100 ⁇ clear filtered sample (sample concentration 1 g / L). The eluent used is tetrahydrofuran with 0.1% by volume of trifluoroacetic acid. The measurement takes place at 25 ° C. As precolumn a column type PSS-SDV, 5 ⁇ , 10 3 A, ID 8.0 mm x 50 mm is used.
  • the columns of the type PSS-SDV, 5 ⁇ , 10 3 ⁇ and 105 ⁇ and 106 ⁇ each with ID 8.0 mm x 300 mm are used (columns of the company Polymer Standards Service, detection by means of differential refractometer Shodex RI71). The flow rate is 1, 0 mL per minute. The calibration is carried out against PMMA standards (polymethyl methacrylate calibration) or (synthetic) rubbers against polystyrene. Density (method R4)
  • the density of the unfoamed and foamed adhesive layers is determined by quotient formation from the application of the composition and the thickness of the adhesive layer applied to a carrier or liner. By measuring the mass of a section of such an adhesive layer applied to a carrier or liner, and defining the mass (known or separately determinable) of the mass, it can measure a section of equal dimensions of the carrier material used.
  • the thickness of the layer can be determined using commercially available thickness measuring devices (probe testing devices) with accuracies of less than 1 ⁇ m deviation. If variations in thickness are detected, the mean value of measurements is given at at least three representative points, that is to say in particular not measured by nicks, folds, specks and the like. Static glass transition temperature T g (method R5)
  • Glass transition points - referred to interchangeably as glass transition temperatures - are reported as the result of differential scanning calorimetry (DSC) measurements in accordance with DIN 53 765 (English: Dynamic Scanning Calorimetry). especially sections 7.1 and 8.1, but with uniform heating and cooling rates of 10 K / min in all heating and cooling steps (see DIN 53 765, section 7.1, note 1).
  • the sample weight is 20 mg.
  • This test serves to quickly test the shear strength of adhesive tapes under temperature load.
  • An adhesive tape cut from the respective sample sample (length approx. 50 mm, width 10 mm) is glued onto a steel test plate cleaned with acetone so that the steel plate projects beyond the adhesive tape to the right and left and the adhesive tape secures the test panel at the upper edge by 2 surmounted.
  • the bonding site is then overrolled six times with a 2 kg steel roller at a speed of 10 m / min.
  • the tape is reinforced flush with a sturdy tape that serves as a support for the distance sensor.
  • the sample is suspended vertically by means of the test plate.
  • the sample to be measured is loaded at the lower end with a weight of 300 g.
  • the test temperature is 40 ° C, the test duration 30 minutes (15 minutes load and 15 minutes unloading).
  • Ball drop test impact method, ball drop
  • method P1 A square, frame-shaped sample was cut out of the adhesive tape to be examined (external dimensions 33 mm ⁇ 33 mm, web width 3.0 mm, internal dimensions (window cutout 27 mm ⁇ 27 mm). This sample was bonded to an ABS frame (external dimensions 45 mm x 45 mm, web width 10 mm, internal dimensions (window cut-out) 25 mm x 25 mm, thickness 3 mm). On the other side of the double-sided adhesive tape was glued a PMMA window of 35 mm x 35 mm. The bonding of ABS frames, adhesive tape frames and PMMA windows was carried out in such a way that the geometric centers and the diagonals overlap one another (corner-to-corner). The bond area was 360 mm 2 . The bond was pressed for 5 s at 10 bar and conditioned for 24 hours at 23 ° C / 50% relative humidity stored.
  • the falling ball test is passed if the bonding has not been resolved in any of the three tests.
  • a rectangular, frame-shaped sample was cut out of the adhesive tape to be examined (outer dimensions 43 mm ⁇ 33 mm, web width in each case 2.0 mm, internal dimensions (window cut-out) 39 mm ⁇ 29 mm, adhesive surface on top and bottom each 288 mm 2 ).
  • PMMA polymethyl methacrylate
  • the full available adhesive surface of the adhesive tape was used.
  • the ABS frames, tape sample and PMMA windows were bonded in such a way that the geometric centers, the bisectors of the acute diagonal angles and the bisectors of the oblique diagonal angles of the rectangles were superimposed (corner-on-corner, long sides on long sides, short sides on short sides).
  • the bond area was 288 mm 2 .
  • the bond was pressed for 5 s at 10 bar and conditioned for 24 hours at 23 ° C / 50% relative humidity stored.
  • a plunger is now moved at a constant speed of 10 mm / min vertically from the top through the window of the ABS frame, so that it centrally on the PMMA Plate presses, and the respective force (determined from the respective pressure and contact surface between the punch and plate) as a function of time from the first contact of the stamp with the PMMA plate until shortly after their fall registered (measuring conditions 23 ° C, 50% relative humidity ).
  • the force acting immediately before the failure of the adhesive bond between the PMMA plate and the ABS frame (maximum force F ma x in the force-time diagram in N) is registered in response to the push-out test.
  • Adhesive force (methods P3: steel and P4: polycarbonate)
  • the determination of the bond strength (according to AFERA 5001) is carried out as follows.
  • the defined primer used is a ground steel plate (ASTM A 666 stainless steel 302, 50 mm 125 mm 1, 1 mm, glossy annealed surface, surface roughness 50 ⁇ 25 nm arithmetic mean deviation from the baseline) or a polycarbonate, respectively.
  • the glued surface element to be examined is cut to a width of 20 mm and a length of about 25 cm, provided with a handling section and immediately thereafter pressed five times with a steel roller of 4 kg at a feed rate of 10 m / min on the selected primer.
  • the measured value (in N / cm) is the average of three individual measurements.
  • the open side of the double-sided adhesive tape to be tested was bonded to a 0.5 mm thick aluminum plate (external dimensions 150 mm x 20 mm) using a rubber roller.
  • the covered side was centered on a 3 mm thick (200 mm x 25 mm external dimensions) PC board.
  • the bond area was 3000 mm 2 .
  • the adhesive composite of PC board adhesive tape and aluminum plate was pressed with a 4 kg hand roller by rolling five times back and forth and stored for 72 hours at 23 ° C / 50% relative humidity.
  • the lifts of the bond between the adhesive tape and the PC board or the adhesive tape and the aluminum plate were measured perpendicularly with a steel linear at the ends of the longitudinal sides of the adhesive bond.
  • the withdrawal for one sample was calculated by taking the mean value from the withdrawal of both sides.
  • the repulsion resistance test shows a further advantage of the adhesive products which were produced with the specific embodiment of the adhesive of the invention (PSA 2 with coordinative and covalent (ie dual) crosslinking) compared with non-dual crosslinked polyacrylate adhesive layers, so that the dual-crosslinked adhesive products are particularly advantageous where it depends on the Repulsionseigenschaften the adhesive product. See Examples 17, 18 in comparison to Examples 19, 20; wherein Examples 17 and 19 or 18 and 20 are each the same thickness.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Toxicology (AREA)
  • General Chemical & Material Sciences (AREA)
  • Adhesives Or Adhesive Processes (AREA)
  • Adhesive Tapes (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne une bande autoadhésive constituée de trois couches, comprenant une couche intérieure (F) composée d'un film support non extensible, une couche (SK1) composée d'une masse adhésive qui est disposée sur une des surfaces de la couche de film support (F) et qui est à base d'une masse d'acrylate expansée, une couche (SK2) composée d'une masse adhésive qui est disposée sur la surface de la couche de film support (F) opposée à la couche (SK1) et qui est à base d'une masse d'acrylate expansée.
EP17706433.4A 2016-06-02 2017-02-16 Bande autoadhésive Active EP3464497B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102016209707.5A DE102016209707A1 (de) 2016-06-02 2016-06-02 Haftklebestreifen
PCT/EP2017/053553 WO2017207119A1 (fr) 2016-06-02 2017-02-16 Bande autoadhésive

Publications (2)

Publication Number Publication Date
EP3464497A1 true EP3464497A1 (fr) 2019-04-10
EP3464497B1 EP3464497B1 (fr) 2022-05-25

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US (1) US20200325362A1 (fr)
EP (1) EP3464497B1 (fr)
JP (1) JP2019523720A (fr)
KR (1) KR102054933B1 (fr)
CN (1) CN109476963B (fr)
DE (1) DE102016209707A1 (fr)
TW (1) TW201809178A (fr)
WO (1) WO2017207119A1 (fr)

Families Citing this family (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP3333235B1 (fr) * 2016-12-09 2023-06-07 tesa SE Bande adhésive
DE102017212854A1 (de) * 2017-07-26 2019-01-31 Tesa Se Bahnförmige, mit Mikroballons geschäumte Haftklebmasse
DE102018200957A1 (de) 2017-10-17 2019-04-18 Tesa Se Haftklebestreifen mit teilgeschäumter Selbstklebemasse
EP3567086B1 (fr) 2018-05-08 2021-08-18 tesa SE Procédé de fabrication d'une couche auto-adhésive expansée par microballons
KR102155172B1 (ko) 2018-05-08 2020-09-11 테사 소시에타스 유로파에아 마이크로벌룬 발포된 자가-접착층을 생성하는 방법
KR102305576B1 (ko) * 2018-10-16 2021-09-27 주식회사 엘지화학 다층 점착 필름
DE102018221356A1 (de) * 2018-12-10 2020-06-10 Tesa Se Mehrschichtiges Klebeband
CN113710762B (zh) * 2019-02-26 2023-08-04 艾利丹尼森公司 具有高剪切和剥离性质的psa组合物
DE102019216938A1 (de) * 2019-11-04 2021-05-06 Tesa Se Geschäumte Haftklebemasseschicht und Klebeband enthaltend die geschäumte Haftklebemasseschicht
KR102313902B1 (ko) * 2020-04-21 2021-10-19 주식회사 영우 압축 성능이 우수한 광경화성 아크릴 폼 점착테이프 및 이의 제조방법
DE102020207783A1 (de) 2020-06-23 2021-12-23 Tesa Se Leitfähiger doppelseitiger Haftklebestreifen
DE102020210505A1 (de) 2020-08-19 2022-02-24 Tesa Se Klebeband mit Polyurethanträger
KR102572211B1 (ko) 2020-08-19 2023-08-28 테사 소시에타스 유로파에아 폴리우레탄 캐리어를 갖는 접착 테이프

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4313008C1 (de) 1993-04-21 1994-11-10 Beiersdorf Ag Selbstklebemasse auf Acrylathotmelt-Basis, Verfahren zu deren Herstellung und deren Verwendung
US6746725B2 (en) * 2000-08-31 2004-06-08 3M Innovative Properties Company Acrylic foam pressure sensitive adhesive method thereof
DE102008004388A1 (de) * 2008-01-14 2009-07-16 Tesa Ag Geschäumte, insbesondere druckempfindliche Klebemasse, Verfahren zur Herstellung sowie die Verwendung derselben
JP2009256607A (ja) * 2008-03-17 2009-11-05 Nitto Denko Corp アクリル系粘着剤、アクリル系粘着剤層、アクリル系粘着テープ又はシート
WO2012152710A2 (fr) * 2011-05-06 2012-11-15 Tesa Se Procédé pour augmenter le pouvoir adhésif d'une couche de matière autoadhésive présentant une surface supérieure et une surface inférieure
DE102013209827A1 (de) * 2012-06-21 2013-12-24 Tesa Se Hitzebeständiges Klebeband
DE102012212883A1 (de) * 2012-07-23 2014-05-15 Tesa Se Geschäumtes Klebeband zur Verklebung auf unpolaren Oberflächen
DE102014207974A1 (de) * 2013-08-02 2015-02-05 Tesa Se Haftklebebänder zur Verklebung von Fenstern insbesondere in Mobilgeräten
DE102013215297A1 (de) * 2013-08-02 2015-02-05 Tesa Se Haftklebemasse
DE102016202479A1 (de) 2016-02-18 2017-08-24 Tesa Se Haftklebestreifen

Also Published As

Publication number Publication date
KR20190012230A (ko) 2019-02-08
JP2019523720A (ja) 2019-08-29
TW201809178A (zh) 2018-03-16
DE102016209707A1 (de) 2017-12-07
CN109476963A (zh) 2019-03-15
KR102054933B1 (ko) 2019-12-11
CN109476963B (zh) 2020-04-14
WO2017207119A1 (fr) 2017-12-07
US20200325362A1 (en) 2020-10-15
EP3464497B1 (fr) 2022-05-25

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